55177-38-3Relevant articles and documents
Photoinduced Copper-Catalyzed Asymmetric C-O Cross-Coupling
Chen, Jia-Rong,Chen, Jun,Guan, Wei,Huan, Xiao-Die,Li, Guo-Qing,Liang, Yu-Jie,Qian, Hao,Wang, Peng-Zi,Xiao, Wen-Jing,Zhang, Bin
supporting information, p. 13382 - 13392 (2021/09/03)
The construction of carbon-heteroatom bonds is one of the most active areas of research in organic chemistry because the function of organic molecules is often derived from the presence of heteroatoms. Although considerable advances have recently been achieved in radical-involved catalytic asymmetric C-N bond formation, there has been little progress in the corresponding C-O bond-forming processes. Here, we describe a photoinduced copper-catalyzed cross-coupling of readily available oxime esters and 1,3-dienes to generate diversely substituted allylic esters with high regio- and enantioselectivity (>75 examples; up to 95% ee). The reaction proceeds at room temperature under excitation by purple light-emitting diodes (LEDs) and features the use of a single, earth-abundant copper-based chiral catalyst as both the photoredox catalyst for radical generation and the source of asymmetric induction in C-O coupling. Combined experimental and density functional theory (DFT) computational studies suggest the formation of π-allylcopper complexes from redox-active oxime esters as bifunctional reagents and 1,3-dienes through a radical-polar crossover process.
Convergent Synthesis of Dihydropyrans from Catalytic Three-Component Reactions of Vinylcyclopropanes, Diazoesters, and Diphenyl Sulfoxide
Zhang, Ya-Lin,Guo, Rui-Ting,Luo, Heng,Liang, Xin-Shen,Wang, Xiao-Chen
supporting information, p. 5627 - 5632 (2020/07/14)
A novel Rh(I)/La(III) cocatalytic three-component reaction of vinylcyclopropanes, diazoesters, and diphenyl sulfoxide has been developed. The reaction gives polysubstituted dihydropyrans as the reaction products. Mechanistic studies indicate that isomerization of vinylcyclopropanes gives conjugated dienes, which then undergo [4 + 2]-cycloaddition with vicinal tricarbonyl compounds generated by oxygen atom transfer from diphenyl sulfoxide to diazoesters.
Highly Selective and Catalytic Generation of Acyclic Quaternary Carbon Stereocenters via Functionalization of 1,3-Dienes with CO2
Chen, Xiao-Wang,Zhu, Lei,Gui, Yong-Yuan,Jing, Ke,Jiang, Yuan-Xu,Bo, Zhi-Yu,Lan, Yu,Li, Jing,Yu, Da-Gang
, p. 18825 - 18835 (2019/11/28)
The catalytic asymmetric functionalization of readily available 1,3-dienes is highly important, but current examples are mostly limited to the construction of tertiary chiral centers. The asymmetric generation of acyclic products containing all-carbon quaternary stereocenters from substituted 1,3-dienes represents a more challenging, but highly desirable, synthetic process for which there are very few examples. Herein, we report the highly selective copper-catalyzed generation of chiral all-carbon acyclic quaternary stereocenters via functionalization of 1,3-dienes with CO2. A variety of readily available 1,1-disubstituted 1,3-dienes, as well as a 1,3,5-triene, undergo reductive hydroxymethylation with high chemo-, regio-, E/Z-, and enantioselectivities. The reported method features good functional group tolerance, is readily scaled up to at least 5 mmol of starting diene, and generates chiral products that are useful building blocks for further derivatization. Systemic mechanistic investigations using density functional theory calculations were performed and provided the first theoretical investigation for an asymmetric transformation involving CO2. These computational results indicate that the 1,2-hydrocupration of 1,3-diene proceeds with high π-facial selectivity to generate an (S)-allylcopper intermediate, which further induces the chirality of the quaternary carbon center in the final product. The 1,4-addition of an internal allylcopper complex, which differs from previous reports involving terminal allylmetallic intermediates, to CO2 kinetically determines the E/Z- and regioselectivity. The rapid reduction of a copper carboxylate intermediate to the corresponding silyl-ether in the presence of Me(MeO)2SiH provides the exergonic impetus and leads to chemoselective hydroxymethylation rather than carboxylation. These results provide new insights for guiding further development of asymmetric C-C bond formations with CO2
